EP0380146B1 - Process for the preparation of n-omega-hydroxyalkyl, n-omega-hydroxy-oxa-alkyl and n-omega-hydroxy-polyoxa-alkyl carbamates - Google Patents
Process for the preparation of n-omega-hydroxyalkyl, n-omega-hydroxy-oxa-alkyl and n-omega-hydroxy-polyoxa-alkyl carbamates Download PDFInfo
- Publication number
- EP0380146B1 EP0380146B1 EP19900105691 EP90105691A EP0380146B1 EP 0380146 B1 EP0380146 B1 EP 0380146B1 EP 19900105691 EP19900105691 EP 19900105691 EP 90105691 A EP90105691 A EP 90105691A EP 0380146 B1 EP0380146 B1 EP 0380146B1
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- European Patent Office
- Prior art keywords
- omega
- alkyl
- hydroxy
- oxa
- polyoxa
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups
Definitions
- the present invention relates to a new process for the preparation of N- ⁇ -hydroxyalkyl, N- ⁇ -hydroxy-oxa-alkyl and N- ⁇ -hydroxy-polyoxa-alkyl-carbamic acid esters of the general formula I HO-A-NHCO2R '(I), in which A represents an alkylene radical, an oxa-alkylene radical or a polyoxa-alkylene radical each having 2 to 12 C atoms and R 'represents an alkyl radical which may have an oxygen atom and has 1 to 6 C atoms.
- the compounds I are intermediates for the preparation of ⁇ -isocyanato-alkyl (meth) acrylates of the general formula II in which R is H- or CH3-, of importance.
- the (meth) acrylates II can be used as starting products for the production of pharmaceuticals and insecticides and as monomers or comonomers for the production of polymers and copolymers.
- Amino alcohols preferred for the new process are those whose alkylene radicals contain 4 to 12, in particular 4 to 8, carbon atoms.
- suitable amino alcohols are 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol, 3-amino-isobutanol, 2-aminobutanol-1, 3-methyl-5-aminopentanol and 2,2-dimethyl -3-aminopropanol-1.
- Suitable oxa-aminoalkanols are, for example, 3-oxa-5-aminopentanol-1, 3-oxa-6-aminohexanol-1, 2,2-dimethyl-4-oxo-7-aminoheptanol and 5-oxa-8-aminooctanol-1.
- 3,6-Dioxa-9-aminononanol-1 may be mentioned as an example of a polyoxaamino alcohol.
- Alkanols containing 1 to 6 carbon atoms, such as methanol, ethanol, propanol, n-butanol, isobutanol and hexanol, are preferably used as alcohols.
- Propanol and butanol are of particular interest.
- cycloalkanols such as, in particular, cyclohexanol and araliphatic alcohols, such as benzyl alcohol and 2-phenylethanol, and also ether alcohols, such as methoxyethanol.
- the reaction generally uses a molar ratio of amino alcohol to urea to alcohol of 1: 0.7 to 5: 1 to 100, preferably 1: 1 to 1.5: 5 to 50. This also applies to the use of amino-oxa alcohols and amino-polyoxa alcohols of the type mentioned.
- the starting components can be mixed in the stated ratio and mostly at temperatures of 170 to 250 ° C, especially at 180 to 235 ° C can be implemented.
- You can work at pressures from 0.1 to 50 bar, depending on the vapor pressure of the used Alcohol, but advantageously a reaction pressure is set such that the reaction mixture boils so that the ammonia formed during the reaction is separated off as completely as possible.
- the separation of ammonia during the reaction can also be supported, for example, by passing indifferent gases through it.
- urea, biuret, triuret, etc. can optionally be used together with urea in the reaction.
- the corresponding carbamic acid esters can also be used, optionally with the addition of alcohol and / or urea.
- the reaction can also be carried out with the addition of small amounts of catalysts.
- catalysts such as come in particular chlorides, bromides, sulfates, phosphates, nitrates, borates, alcoholates, phenates, sulfonates, oxides, oxide hydrates, hydroxides, carboxylates, chelate compounds, carbonates, thiocarbamates and dithiocarbamates, preferably of lithium, calcium, aluminum, tin, bismuth, antimony , Copper, zinc, titanium, vanadium, chromium, molybdenum, manganese, iron, nickel and cobalt. Compounds of iron, cobalt, nickel, zinc, tin and titanium are of particular interest.
- Such catalysts can generally be used in amounts of from 0.0001 to 0.1, preferably from 0.0005 to 0.05, equivalent metal ion, based on the amino alcohol.
- the desired N- ⁇ -hydroxyalkyl, N- ⁇ -hydroxy-oxa-alkyl or N- ⁇ -hydroxy-polyoxa-alkyl-carbamic acid esters formed by the new process can, after distilling off excess alcohol and any by-products, by distillation in vacuo or be cleaned by crystallization.
- N- ⁇ -hydroxyalkyl, N- ⁇ -hydroxy-oxa-alkyl or N- ⁇ -hydroxy-polyoxa-alkyl-carbamic acid esters obtainable in this way can be esterified by reaction with (meth) acrylic acid alkyl esters or (meth) acrylic acid anhydride and the resulting products obtained ⁇ -Alkoxicarbamoyl-alkyl, -oxa-alkyl and -polyoxa-alkyl (meth) acrylates are cleaved by heating in compounds II and alcohol.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Description
Die vorliegende Erfindung betrifft ein neues Verfahren zur Herstellung von N-ω-Hydroxialkyl-, N-ω-Hydroxi-oxa-alkyl- und N-ω-Hydroxi-polyoxa-alkyl-carbaminsäureestern der allgemeinen Formel I
HO-A-NHCO₂R' (I),
in der A für einen Alkylenrest, einen Oxa-alkylenrest oder einen Polyoxa-alkylenrest mit jeweils 2 bis 12 C-Atomen und R' für einen gegebenenfalls ein Sauerstoffatom enthaltenden Alkylrest mit 1 bis 6 C-Atomen stehen.The present invention relates to a new process for the preparation of N-ω-hydroxyalkyl, N-ω-hydroxy-oxa-alkyl and N-ω-hydroxy-polyoxa-alkyl-carbamic acid esters of the general formula I
HO-A-NHCO₂R '(I),
in which A represents an alkylene radical, an oxa-alkylene radical or a polyoxa-alkylene radical each having 2 to 12 C atoms and R 'represents an alkyl radical which may have an oxygen atom and has 1 to 6 C atoms.
Die Verbindungen I sind als Zwischenprodukte zur Herstellung von ω-Isocyanato-alkyl-(meth)-acrylaten der allgemeinen Formel II
in der R für H- oder CH₃- steht, von Bedeutung. Die (Meth)acrylate II können als Ausgangsprodukte zur Herstellung von Pharmazeutika und Insektiziden sowie als Monomere bzw. Comonomere für die Herstellung von Polymerisaten und Copolymerisaten eingesetzt werden.The compounds I are intermediates for the preparation of ω-isocyanato-alkyl (meth) acrylates of the general formula II
in which R is H- or CH₃-, of importance. The (meth) acrylates II can be used as starting products for the production of pharmaceuticals and insecticides and as monomers or comonomers for the production of polymers and copolymers.
Bisher wurden die Verbindungen I meist durch Umsetzen von Aminoalkanolen mit Chlorkohlensäureestern gewonnen. So offenbart z.B. die US-PS 2 485 855 die Herstellung des 2-Hydroxiethylcarbaminsäureethylesters aus 2-Aminoethanol und Chlorkohlensäureethylester. Nach Iwakura (Chem. High Polymers Japan 2 (1945), 305) erhält man beim Erwärmen von 6-Hydroxihexanoylazid mit Ethanol in Benzol N-(5-Hydroxipentyl)carbaminsäureethylester. Die US-PS 1 927 858 schließlich lehrt die Bildung von N-Hydroxialkylcarbaminsäureestern aus Aminoalkoholen und Dialkylcarbonaten. Nachteilig an allen vorgenannten Verfahren ist, daß sie verhältnismäßig toxische und teure Edukte verwenden.So far, the compounds I have mostly been obtained by reacting aminoalkanols with chlorocarbonic acid esters. For example, US Pat. No. 2,485,855 the preparation of the 2-hydroxyethylcarbamic acid ethyl ester from 2-aminoethanol and chlorinated carbonate. According to Iwakura (Chem. High Polymers Japan 2 (1945), 305), heating 6-hydroxihexanoylazide with ethanol in benzene gives N- (5-hydroxipentyl) carbamic acid ethyl ester. Finally, US Pat. No. 1,927,858 teaches the formation of N-hydroxyalkylcarbamic acid esters from amino alcohols and dialkyl carbonates. A disadvantage of all of the aforementioned processes is that they use relatively toxic and expensive starting materials.
Aufgabe der vorliegenden Erfindung war es, diesem Nachteil abzuhelfen. Demgemäß wurde ein neues Verfahren zur Herstellung von Verbindungen I gefunden, das dadurch gekennzeichnet ist, daß man einen Aminoalkohol der allgemeinen Formel III
HO-A-NH₂ (III),
mit Harnstoff und einem Alkohol der allgemeinen Formel IV
R'OH (IV),
zu einer Verbindung I umsetzt.The object of the present invention was to remedy this disadvantage. Accordingly, a new process for the preparation of compounds I found, which is characterized in that an amino alcohol of the general formula III
HO-A-NH₂ (III),
with urea and an alcohol of the general formula IV
R'OH (IV),
to a compound I converts.
Es ist überraschend, daß die Verbindungen I nach dem erfindungsgemäßen Verfahren in guter Ausbeute erhalten werden, zumal im Hinblick auf die Bifunktionalität der Aminoalkoholkomponente eine Vielzahl verschiedener Reaktionsprodukte denkbar ist. Selbst bei Verwendung von Aminoethanol und Aminopropanol, wo durch Ringschluß die ausschließliche Bildung von 2-Oxo-tetrahydro-1,3-oxazolidin bzw. 2-Oxo-tetrahydro-1,3-oxazin zu erwarten war, wurden die gewünschten Carbaminsäureester, nämlich der N-(2-Hydroxiethyl)-bzw. N-(3-Hydroxipropyl)-carbaminsäureester in befriedigenden Ausbeuten erhalten.It is surprising that the compounds I are obtained in good yield by the process according to the invention, especially since a large number of different reaction products is conceivable in view of the bifunctionality of the amino alcohol component. Even when using aminoethanol and aminopropanol, where the exclusive formation of 2-oxo-tetrahydro-1,3-oxazolidine or 2-oxo-tetrahydro-1,3-oxazine was to be expected by ring closure, the desired carbamic acid esters, namely the N- (2-hydroxyethyl) or Obtain N- (3-hydroxypropyl) carbamic acid ester in satisfactory yields.
Als Aminoalkohole werden für das neue Verfahren solche vorgezogen, deren Alkylenreste 4 bis 12, insbesondere 4 bis 8 C-Atome enthalten. Beispiele für geeignete Aminoalkohole sind 2-Aminoethanol, 3-Aminopropanol, 4-Aminobutanol, 5-Aminopentanol, 6-Aminohexanol, 3-Amino-isobutanol, 2-Aminobutanol-1, 3-Methyl-5-aminopentanol und 2,2-Dimethyl-3-aminopropanol-1. Geeignete Oxa-aminoalkanole sind z.B. 3-Oxa-5-aminopentanol-1, 3-Oxa-6-aminohexanol-1, 2,2-Dimethyl-4-oxo-7-aminoheptanol und 5-Oxa-8-aminooctanol-1. Als Polyoxaaminoalkohol sei beispielhaft 3,6-Dioxa-9-aminononanol-1 genannt. Als Alkohole werden vorzugsweise 1 bis 6 C-Atome enthaltende Alkanole, wie Methanol, Ethanol, Propanol, n-Butanol, Isobutanol und Hexanol eingesetzt. Von besonderem Interesse sind Propanol und Butanol. Ferner geeignet als Alkoholkomponente sind Cycloalkanole wie besonders Cyclohexanol und araliphatische Alkohole, wie Benzylalkohol und 2-Phenylethanol sowie ferner Etheralkohole wie Methoxiethanol. Bei der Umsetzung wendet man im allgemeinen ein Molverhältnis von Aminoalkohol zu Harnstoff zu Alkohol von 1:0,7 bis 5:1 bis 100, vorzugsweise von 1:1 bis 1,5:5 bis 50 an. Dies gilt auch beim Einsatz von Amino-oxa-alkoholen und Amino-polyoxa-alkoholen der genannten Art. Sei der praktischen Durchführung des Verfahrens können die Ausgangskomponenten in dem angegebenen Verhältnis vermischt und meist bei Temperaturen von 170 bis 250°C, insbesondere bei 180 bis 235°C umgesetzt werden. Dabei kann man bei Drücken von 0,1 bis 50 bar arbeiten, entsprechend dem Dampfdruck des verwendeten Alkohols, doch wird vorteilhaft ein Reaktionsdruck eingestellt derart, daß die Reaktionsmischung siedet, damit der bei der Reaktion entstehende Ammoniak möglichst vollständig abgetrennt wird. Das Abtrennen von Ammoniak während der Reaktion kann auch z.B. durch Hindurchleiten von indifferenten Gasen unterstützt werden. Anstelle von Harnstoffen kann bei der Reaktion auch Biuret, Triuret usw. gegebenenfalls zusammen mit Harnstoff eingesetzt werden. Anstelle von Harnstoff und Alkohol kann man auch die entsprechenden Carbaminsäureester, gegebenenfalls unter Zusatz von Alkohol und/oder Harnstoff einsetzen.Amino alcohols preferred for the new process are those whose alkylene radicals contain 4 to 12, in particular 4 to 8, carbon atoms. Examples of suitable amino alcohols are 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol, 3-amino-isobutanol, 2-aminobutanol-1, 3-methyl-5-aminopentanol and 2,2-dimethyl -3-aminopropanol-1. Suitable oxa-aminoalkanols are, for example, 3-oxa-5-aminopentanol-1, 3-oxa-6-aminohexanol-1, 2,2-dimethyl-4-oxo-7-aminoheptanol and 5-oxa-8-aminooctanol-1. 3,6-Dioxa-9-aminononanol-1 may be mentioned as an example of a polyoxaamino alcohol. Alkanols containing 1 to 6 carbon atoms, such as methanol, ethanol, propanol, n-butanol, isobutanol and hexanol, are preferably used as alcohols. Propanol and butanol are of particular interest. Also suitable as an alcohol component are cycloalkanols, such as, in particular, cyclohexanol and araliphatic alcohols, such as benzyl alcohol and 2-phenylethanol, and also ether alcohols, such as methoxyethanol. The reaction generally uses a molar ratio of amino alcohol to urea to alcohol of 1: 0.7 to 5: 1 to 100, preferably 1: 1 to 1.5: 5 to 50. This also applies to the use of amino-oxa alcohols and amino-polyoxa alcohols of the type mentioned. Be the practical implementation of the process, the starting components can be mixed in the stated ratio and mostly at temperatures of 170 to 250 ° C, especially at 180 to 235 ° C can be implemented. You can work at pressures from 0.1 to 50 bar, depending on the vapor pressure of the used Alcohol, but advantageously a reaction pressure is set such that the reaction mixture boils so that the ammonia formed during the reaction is separated off as completely as possible. The separation of ammonia during the reaction can also be supported, for example, by passing indifferent gases through it. Instead of urea, biuret, triuret, etc. can optionally be used together with urea in the reaction. Instead of urea and alcohol, the corresponding carbamic acid esters can also be used, optionally with the addition of alcohol and / or urea.
Bei dem Verfahren kann man die Umsetzung auch unter Zusatz geringer Mengen Katalysatoren durchführen. Als solche kommen besonders Chloride, Bromide, Sulfate, Phosphate, Nitrate, Borate, Alkoholate, Phenolate, Sulfonate, Oxide, Oxidhydrate, Hydroxide, Carboxilate, Chelatverbindungen, Carbonate, Thiocarbamate und Dithiocarbamate vorzugsweise des Lithiums, Calciums, Aluminiums, Zinns, Wismuts, Antimons, Kupfers, Zinks, Titans, Vanadins, Chroms, Molybdäns, Mangans, Eisens, Nickels und Kobalts in Frage. Von besonderem Interesse sind Verbindungen von Eisen, Kobalt, Nickel, Zink, Zinn und Titan.In the process, the reaction can also be carried out with the addition of small amounts of catalysts. Such as come in particular chlorides, bromides, sulfates, phosphates, nitrates, borates, alcoholates, phenates, sulfonates, oxides, oxide hydrates, hydroxides, carboxylates, chelate compounds, carbonates, thiocarbamates and dithiocarbamates, preferably of lithium, calcium, aluminum, tin, bismuth, antimony , Copper, zinc, titanium, vanadium, chromium, molybdenum, manganese, iron, nickel and cobalt. Compounds of iron, cobalt, nickel, zinc, tin and titanium are of particular interest.
Derartige Katalysatoren können im allgemeinen in Mengen von 0,0001 bis 0,1, vorzugsweise von 0,0005 bis 0,05 äquivalent Metallion, bezogen auf den Aminoalkohol eingesetzt werden.Such catalysts can generally be used in amounts of from 0.0001 to 0.1, preferably from 0.0005 to 0.05, equivalent metal ion, based on the amino alcohol.
Die nach dem neuen Verfahren gebildeten gewünschten N-ω-Hydroxialkyl-, N-ω-Hydroxi-oxa-alkyl- oder N-ω-Hydroxi-polyoxa-alkyl-carbaminsäureester können nach Abdestillieren von überschüssigem Alkohol und eventuellen Nebeprodukten durch Destillation im Vakuum oder durch Kristallisation gereinigt wreden.The desired N-ω-hydroxyalkyl, N-ω-hydroxy-oxa-alkyl or N-ω-hydroxy-polyoxa-alkyl-carbamic acid esters formed by the new process can, after distilling off excess alcohol and any by-products, by distillation in vacuo or be cleaned by crystallization.
Die so erhältlichen N-ω-Hydroxialkyl-, N-ω-Hydroxi-oxa-alkyl- oder N-ω-Hydroxi-polyoxa-alkyl-carbaminsäureester können durch Umsetzen mit (Meth)acrylsäurealkylestern oder (Meth)acrylsäureanhydrid verestert und die dabei erhaltenen ω-Alkoxicarbamoyl-alkyl-, -oxa-alkyl- und -polyoxa-alkyl(meth)acrylate durch Erhitzen in Verbindungen II und Alkohol gespalten werden.The N-ω-hydroxyalkyl, N-ω-hydroxy-oxa-alkyl or N-ω-hydroxy-polyoxa-alkyl-carbamic acid esters obtainable in this way can be esterified by reaction with (meth) acrylic acid alkyl esters or (meth) acrylic acid anhydride and the resulting products obtained ω-Alkoxicarbamoyl-alkyl, -oxa-alkyl and -polyoxa-alkyl (meth) acrylates are cleaved by heating in compounds II and alcohol.
In einem 1 l-Rührautoklaven mit aufgesetzter Druckkolonne und Druckregelventil werden 35,6 g 4-Aminobutanol, 26,4 g Harnstoff, 592 g n-Butanol und 68 mg Zinn(II)chlorid 5 Stunden bei 5 bar unter Rückfluß und Abnahme von Ammoniak gekocht. Man erhielt 636 g einer gelblichen Flüssigkeit. Eine Analyse des Reaktionsgemisches (Gelpermeationschromatographie, Methode des externen Standards) zeigte, daß die Umwandlung in N-(4-Hydroxibutyl)-carbaminsäurebutylester 84 % betrug.35.6 g of 4-aminobutanol, 26.4 g of urea, 592 g of n-butanol and 68 mg of tin (II) chloride are refluxed for 5 hours at 5 bar in a 1 liter stirred autoclave with a pressure column and pressure control valve Boiled ammonia. 636 g of a yellowish liquid were obtained. Analysis of the reaction mixture (gel permeation chromatography, external standard method) showed that the conversion to butyl N- (4-hydroxibutyl) carbamate was 84%.
Nach Abdestillieren von überschüssigem Butanol und Carbaminsäurebutylester wurde der Rückstand über einen Dünnschichtverdampfer destilliert. Das Produkt geht bei 140°C/0,1 mbar über und erstarrt in der Vorlage kristallin. Es wurden 59,7 g (79 %) N-(4-Hydroxibutyl)carbaminsäureester (Reinheit > 99 %) erhalten. Eine Probe wurde aus Essigsäureethylester umkristallisiert und schmilzt bei 51°C.After distilling off excess butanol and carbamic acid butyl ester, the residue was distilled using a thin-film evaporator. The product passes at 140 ° C / 0.1 mbar and solidifies crystalline in the initial charge. 59.7 g (79%) of N- (4-hydroxibutyl) carbamic acid ester (purity> 99%) were obtained. A sample was recrystallized from ethyl acetate and melted at 51 ° C.
In einem 1 l-Rührautoklaven mit aufgesetzter Druckkolonne und Druckregelventil werden 42 g 5-Amino-3-oxapentanol, 26,4 g Harnstoff, 592 g n-Butanol 2 Stunden bei 230°C und 16 bar unter Abnahme von Ammoniak am Rückfluß gekocht. Man erhielt 628 g einer gelblichen Flüssigkeit, deren Analyse mittels Gelpermeationschromatographie eine Umwandlung von 92 % anzeigte. Nach Abdestillieren von überschüssigem Butanol und Carbamat wurde der Rückstand von vier Ansätzen destilliert. Das Produkt geht bei 132°C/0,1 mbar über. Es wurden 286 g (87 %) N-(5-Hydroxi-3-oxapentyl)carbaminsäurebutylester erhalten.42 g of 5-amino-3-oxapentanol, 26.4 g of urea, 592 g of n-butanol are boiled under reflux for 2 hours at 230 ° C. and 16 bar in a 1 l stirred autoclave with a pressure column and pressure control valve. 628 g of a yellowish liquid were obtained, the analysis of which by gel permeation chromatography indicated a conversion of 92%. After distilling off excess butanol and carbamate, the residue was distilled from four batches. The product passes at 132 ° C / 0.1 mbar. 286 g (87%) of N- (5-hydroxy-3-oxapentyl) carbamic acid butyl ester were obtained.
Claims (3)
- A process for preparing compounds of the formula I
HO-A-NHCO₂R' (I)
where A is alkylene, oxa-alkylene or polyoxa-alkylene with, in each case, 2-12 carbon atoms and R' is alkyl which has 1-6 carbon atoms and may contain an oxygen atom, which comprises reacting an amino alcohol of the formula III
HO-A-NH₂ (III)
with urea and an alcohol of the formula IV
R'OH (IV)
at from 170 to 250°C with removal of ammonia. - A process as claimed in claim 1, wherein the reaction is carried out at from 180 to 235°C.
- A process as claimed in claim 1 or 2, wherein the amino alcohol III:urea:alcohol IV molar ratio is 1:1-1.5:5-50.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19853523692 DE3523692A1 (en) | 1985-07-03 | 1985-07-03 | METHOD FOR PRODUCING (OMEGA) -ISOCYANATOALKYL (METH) ACRYLATES |
| DE3523692 | 1985-07-03 |
Related Parent Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP86108777.3 Division | 1986-06-27 | ||
| EP19860108777 Division EP0207461B1 (en) | 1985-07-03 | 1986-06-27 | Process for the preparation of omega-isocyanatoalkyl(meth)acrylates |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0380146A2 EP0380146A2 (en) | 1990-08-01 |
| EP0380146A3 EP0380146A3 (en) | 1991-01-09 |
| EP0380146B1 true EP0380146B1 (en) | 1993-08-18 |
Family
ID=6274786
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19900105691 Expired - Lifetime EP0380146B1 (en) | 1985-07-03 | 1986-06-27 | Process for the preparation of n-omega-hydroxyalkyl, n-omega-hydroxy-oxa-alkyl and n-omega-hydroxy-polyoxa-alkyl carbamates |
| EP19860108777 Expired - Lifetime EP0207461B1 (en) | 1985-07-03 | 1986-06-27 | Process for the preparation of omega-isocyanatoalkyl(meth)acrylates |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19860108777 Expired - Lifetime EP0207461B1 (en) | 1985-07-03 | 1986-06-27 | Process for the preparation of omega-isocyanatoalkyl(meth)acrylates |
Country Status (3)
| Country | Link |
|---|---|
| EP (2) | EP0380146B1 (en) |
| JP (1) | JPH0637454B2 (en) |
| DE (3) | DE3523692A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6838530B2 (en) | 2001-11-29 | 2005-01-04 | Basf Corporation | Method of preparing various multifunctional materials using limited starting reactants |
| US7122605B2 (en) | 2001-11-29 | 2006-10-17 | Basf Corporation | Method for selective graft polymerization |
| US6825286B2 (en) | 2001-11-29 | 2004-11-30 | Basf Corporation | Method for determining the water solubility or water dispersibility of waterborne beta-hydroxy primary carbamate functional graft materials |
| US6812300B2 (en) * | 2001-11-29 | 2004-11-02 | Basf Corporation | Method for making multifunctional materials |
| EP2163540B1 (en) * | 2007-05-21 | 2014-01-08 | Showa Denko K.K. | Method for producing ethylenically unsaturated group-containing isocyanate compound having ether bond |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1927858A (en) | 1930-12-27 | 1933-09-26 | Ig Farbenindustrie Ag | Urethane derivatives and alpha process for their production |
| US2485855A (en) | 1944-12-30 | 1949-10-25 | Us Seeretary Of The Navy | Nitramines |
| US2718516A (en) * | 1952-11-08 | 1955-09-20 | Rohm & Haas | Isocyanato esters of acrylic, methacrylic, and crotonic acids |
| DE2943481A1 (en) * | 1979-10-27 | 1981-05-07 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING URETHANES AND THE USE THEREOF FOR PRODUCING ISOCYANATES |
| JPH021945A (en) | 1988-06-09 | 1990-01-08 | Sharp Corp | Manufacture of semiconductor device |
-
1985
- 1985-07-03 DE DE19853523692 patent/DE3523692A1/en not_active Withdrawn
-
1986
- 1986-06-27 EP EP19900105691 patent/EP0380146B1/en not_active Expired - Lifetime
- 1986-06-27 DE DE8686108777T patent/DE3677833D1/en not_active Expired - Lifetime
- 1986-06-27 JP JP61149883A patent/JPH0637454B2/en not_active Expired - Lifetime
- 1986-06-27 EP EP19860108777 patent/EP0207461B1/en not_active Expired - Lifetime
- 1986-06-27 DE DE9090105691T patent/DE3688912D1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0380146A2 (en) | 1990-08-01 |
| DE3677833D1 (en) | 1991-04-11 |
| EP0207461A3 (en) | 1987-12-09 |
| EP0207461A2 (en) | 1987-01-07 |
| EP0380146A3 (en) | 1991-01-09 |
| JPH0637454B2 (en) | 1994-05-18 |
| EP0207461B1 (en) | 1991-03-06 |
| DE3523692A1 (en) | 1987-01-08 |
| DE3688912D1 (en) | 1993-09-23 |
| JPS6210053A (en) | 1987-01-19 |
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